WO2021200358A1 - 積層ポリエステル樹脂被覆金属板、積層ポリエステル樹脂フィルム、及び缶蓋 - Google Patents

積層ポリエステル樹脂被覆金属板、積層ポリエステル樹脂フィルム、及び缶蓋 Download PDF

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WO2021200358A1
WO2021200358A1 PCT/JP2021/011836 JP2021011836W WO2021200358A1 WO 2021200358 A1 WO2021200358 A1 WO 2021200358A1 JP 2021011836 W JP2021011836 W JP 2021011836W WO 2021200358 A1 WO2021200358 A1 WO 2021200358A1
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Prior art keywords
polyester resin
metal plate
coated metal
laminated polyester
component
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PCT/JP2021/011836
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English (en)
French (fr)
Japanese (ja)
Inventor
悟史 河村
優斗 佐藤
伊藤　由実
Original Assignee
東洋鋼鈑株式会社
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Application filed by 東洋鋼鈑株式会社 filed Critical 東洋鋼鈑株式会社
Priority to US17/907,447 priority Critical patent/US20230132293A1/en
Priority to EP21779255.5A priority patent/EP4129647A4/en
Priority to CN202180021038.5A priority patent/CN115298025A/zh
Publication of WO2021200358A1 publication Critical patent/WO2021200358A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B32B2264/1021—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/30—Particles characterised by physical dimension
    • B32B2264/301—Average diameter smaller than 100 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2435/00—Closures, end caps, stoppers
    • B32B2435/02—Closures, end caps, stoppers for containers

Definitions

  • the present invention relates to a laminated polyester resin-coated metal plate, a laminated polyester resin film for laminating a metal plate, and a can lid using them.
  • a stayion tab (SOT) type that can be easily opened by hand and the opening is left attached to the can body, or the opening is separated from the can body.
  • Easy-open (EO) lids such as tear-off type lids are widely used.
  • a resin-coated metal plate obtained by forming a resin layer such as polyester resin on a metal base material such as aluminum or steel is known.
  • Patent Document 1 discloses a resin-coated metal plate for the purpose of suppressing the occurrence of a feathering phenomenon when formed on a lid and improving characteristics such as openness.
  • the resin-coated metal plate disclosed in Patent Document 1 As the resin layer laminated on the metal plate, the lower layer in which the olefin polymer is blended with the thermoplastic polyester resin and the crystallinity of the thermoplastic polyester are controlled. A multi-layered resin layer having a surface layer having an elongation of 20% is disclosed. As described above, in Patent Document 1, the resin layer is multi-layered for the purpose of achieving both corrosion resistance and processability. However, in the technique of Patent Document 1, there remains a problem regarding openness (feathering resistance).
  • the resin layer is cut along the score formed on the can lid. That is, it is required to avoid the occurrence of delamination between the metal base material and the resin layer in the opening portion and the phenomenon (feathering phenomenon) in which the stretched inner surface side coating resin remains in the vicinity of the opening portion. In order to improve this openness, it is considered necessary to suppress the softness (elongation) of the resin to some extent.
  • can lids are generally subjected to rib processing for reinforcement and overhang drawing processing as rivet parts, so the resin layer follows the above processing for metal substrates. I need to be able to do it. Further, when the above processing is performed in a heat treatment process such as printing, it is necessary to avoid the occurrence of film cracking, peeling, etc. at the place where the processing is large as described above. And in order to improve such workability, it is necessary that the resin used is soft to some extent. That is, it can be said that the above-mentioned processability and openness are contradictory characteristics, and there has been a demand for the development of a resin that has both of these characteristics in a can lid using a resin-coated metal plate.
  • the present inventors have diligently studied to solve the above problems. As a result, in a laminated polyester resin film for manufacturing a can lid and a laminated polyester resin-coated metal plate, it was found that the above problems can be compatible at a high level by setting the resin layer structure to a predetermined value, and the present invention was conceived. It was done.
  • the laminated polyester resin-coated metal plate includes (1) a metal base material and a laminated polyester resin layer formed on at least one surface of the metal base material.
  • the laminated polyester resin layer contains, in order from the metal base material side, a lower layer made of a polyester resin (A) modified with 2 to 30 mol% of the first copolymerization component, a polyester resin (B), and the polyester resin.
  • the soft component (C) that is incompatible with (B) is contained and the total of the polyester resin (B) and the soft component (C) is 100% by mass
  • the content of the soft component (C) is 2 to 50. It is characterized by having an upper layer which is by mass%.
  • the laminated polyester resin-coated metal plate according to (1) described above is (2) the polyester resin (B) is a thermoplastic polyester resin having a glass transition temperature (Tg1) of 60 ° C. or higher and 90 ° C. or lower, and is flexible.
  • the component (C) is either or both of a polyester-based thermoplastic elastomer and a polyolefin, and the soft component (C) is dispersed in the polyester resin (B), and is in the upper layer of the soft component (C).
  • the absolute value ⁇ Tg of the difference between the glass transition temperature (Tg1) of the polyester resin (B) and the glass transition temperature (Tg2) of the upper layer is ⁇ Tg ⁇ 0.5 ⁇ W. It is preferable to satisfy.
  • the flexible component (C) is dispersed in the polyester resin (B) in an island shape, and the islands are dispersed.
  • the average major axis of the flexible component (C) dispersed in the shape is preferably 0.1 to 5.0 ⁇ m, and the average minor axis is preferably 0.01 to 2 ⁇ m.
  • the polyester resin (A) is mainly composed of polyethylene terephthalate, and isophthalic acid is used as the first copolymerization component. Is preferably included.
  • the laminated polyester resin-coated metal plate according to (4) described above further contains (5) a polyfunctional component in which the lower layer is 0.01 to 0.5 mol%.
  • the laminated polyester resin-coated metal plate according to any one of (1) to (5) described above preferably has (6) a weight average molecular weight of the polyester resin (A) of 40,000 to 80,000.
  • the polyester resin (A) contains inorganic particles having an average particle size of 0.2 to 5.0 ⁇ m. It is preferably contained in an amount of 0.1 to 5.0% by mass.
  • the total thickness of the upper layer and the lower layer is 10 to 50 ⁇ m, and the thickness of the upper layer is 10 to 50 ⁇ m. Is 5 to 40 ⁇ m, and the thickness of the lower layer is preferably 5 to 30 ⁇ m.
  • the lower layer has a elongation at break in an environment of 50 ° C. after heat treatment at 185 ° C. for 10 minutes. Is preferably 50% or less.
  • the laminated polyester resin-coated metal plate according to any one of (1) to (9) described above is formed on the side opposite to the metal base material side of the upper layer (10), and further forms a surface layer made of polyester resin. It is preferable to have.
  • the laminated polyester resin film in one embodiment of the present invention was formed on at least one surface of the (11) metal substrate and modified with 2 to 30 mol% of the first copolymerization component.
  • a lower layer made of a polyester resin (A), a soft component (C) formed on the lower layer and incompatible with the polyester resin (B) and the polyester resin (B), and the polyester resin (B). It is characterized by having an upper layer in which the content of the soft component (C) is 2 to 50% by mass when the total of the soft components (C) is 100% by mass.
  • the can lid in one embodiment of the present invention is (12) using the laminated polyester resin-coated metal plate according to any one of (1) to (10) described above.
  • the can lid in another embodiment of the present invention is made of (13) the laminated polyester resin film described in (11) above.
  • the lamination in addition to the openness at the time of opening, which is suitable for use as a can lid, for example, the lamination has a high degree of suppression of film cracking (processability) in the vicinity of the rivet portion provided on the can lid.
  • a polyester resin-coated metal plate, a laminated polyester resin film, and a can lid can be realized. Further, according to the laminated polyester resin-coated metal plate, the laminated polyester resin film, and the can lid of the present invention, suppression of resin peeling (adhesion) after retort treatment after filling the contents, and a metal base material after aging. It is possible to provide each performance of corrosion suppression (corrosion resistance).
  • FIG. 1 is a schematic view showing a cross section of the laminated polyester resin-coated metal plate 100 of the present embodiment.
  • the laminated polyester resin-coated metal plate, the laminated polyester resin film, and the can lid of the present invention will be described using the embodiments, but the present invention is not limited to the following embodiments.
  • the laminated polyester resin-coated metal plate 100 of the present embodiment has a metal base material MP and a laminated polyester resin layer 200 formed on at least one surface of the metal base material MP.
  • the laminated polyester resin layer 200 includes a lower layer 10 and an upper layer 20 which are sequentially formed on the metal base material MP.
  • the laminated polyester resin-coated metal plate 100 of the present embodiment is formed on at least one surface of the metal base material MP and the metal base material MP, and is modified with 2 to 30 mol% of the first copolymerization component.
  • the polyester resin (A) is formed on the lower layer 10 on the side close to the metal base material MP and on the lower layer 10 (the side opposite to the metal base material MP side), and the polyester resin (B) and the polyester resin (
  • the soft component (C) which is incompatible with B) is contained and the total of the polyester resin (B) and the soft component (C) is 100% by mass
  • the content of the soft component (C) is 2 to 50. It has an upper layer 20 which is a mass%.
  • the laminated polyester resin-coated metal plate 100 of the present embodiment is not limited to the two-layer structure of the lower layer 10 and the upper layer 20 as shown in FIG. 1, and may have a structure of three or more layers as described in detail later.
  • Metal base material MP used for the laminated polyester resin-coated metal plate 100 of the present embodiment a known metal base material MP such as an aluminum material or a steel plate conventionally used for an easy-open lid can be used.
  • the thickness of the aluminum material varies depending on the size of the lid and the like, but it is generally preferably in the range of 0.20 to 0.50 mm, particularly 0.23 to 0.30 mm. Further, a surface treatment film such as chromate treatment, zirconium treatment, phosphoric acid treatment, or polyacrylic acid treatment may be formed on the surface of the aluminum material.
  • the steel sheet various known steel sheets such as a chromate surface-treated steel sheet such as TFS (tin-free steel) and a fluffy steel sheet plated with a tin plating amount of 0.3 to 2.8 g / m 2 can be preferably used. ..
  • the thickness of the steel sheet is preferably in the range of 0.1 to 0.4 mm, particularly 0.12 to 0.35 mm.
  • the lower layer 10 of the laminated polyester resin-coated metal plate 100 of the present embodiment will be described. As shown in FIG. 1, the lower layer 10 is formed on at least one surface of the metal base material MP. Then, of the lower layer 10 and the upper layer 20 of the laminated polyester resin layer 200 described later, the lower layer 10 is formed closer to the metal base material MP.
  • the polyester resin (A) applied to the lower layer 10 of the laminated polyester resin-coated metal plate 100 of the present embodiment is a copolymerized polyester resin, which is modified with 2 to 30 mol% of the first copolymerized component.
  • the polyester resin (A) is preferably a copolymer resin mainly composed of polyethylene terephthalate.
  • the above-mentioned first copolymerization component examples include isophthalic acid (IA), orthophthalic acid, p- ( ⁇ -hydroxyethoxy) benzoic acid, naphthalene 2,6-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, and the like. At least one selected from the group consisting of 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, adipic acid, sebacic acid, trimellitic acid and pyromellitic acid can be mentioned. Of these, the above-mentioned first copolymerization component is preferably isophthalic acid from the viewpoint of processability and adhesion.
  • these first copolymerization components are contained in the copolymerized polyester resin of the lower layer 10 in an amount of 2 to 30 mol%. If the first copolymerization component is less than 2 mol%, the adhesion between the metal base material MP and the lower layer 10 may decrease, which is not preferable. On the other hand, when the amount of the first copolymerization component exceeds 30 mol%, it is not economically preferable and it is not preferable because the film-forming property and the barrier property of the lower layer 10 may be deteriorated.
  • the amount of the first copolymerization component in the copolymerized polyester resin of the lower layer 10 is more preferably 5 to 15 mol%.
  • the glycol components contained include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, and 1 , 6-Hexylene glycol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, etc., or two or more thereof can be mentioned.
  • the copolymerized polyester resin in the lower layer 10 preferably further contains a second copolymerization component (polyfunctional component) different from the first copolymerization component in an amount of 0.01 to 0.5 mol%.
  • This polyfunctional component is introduced for the purpose of introducing a crosslinked structure and improving openness.
  • gel is likely to be generated in the copolymerized polyester resin of the lower layer 10, and it is preferable from the economical viewpoint. No.
  • polyfunctional component examples include one or more selected from trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, trimethylolpropane, and pentaerythritol.
  • trimellitic acid (TMA) or pentaerythritol is particularly preferable from the viewpoint of easy availability.
  • the weight average molecular weight of the lower copolymer polyester resin is preferably 40,000 to 80,000 from the viewpoint of adjusting the viscosity of the lower layer resin and improving the openness. If the weight average molecular weight is less than 40,000, the film-forming property of the resin layer may be deteriorated, which is not preferable. On the other hand, when the weight average molecular weight exceeds 80,000, the torque in the kneader may become too high when the resin layer is formed, which is not preferable. It is more preferable that the weight average molecular weight is 40,000 to 55,000 from the same viewpoint.
  • the lower copolymer polyester resin contains 0.1 to 5.0% by mass of inorganic particles having an average particle size of 0.2 ⁇ m to 5.0 ⁇ m, which improves the winding shape of the film. , It is preferable from the viewpoint of avoiding the occurrence of film wrinkles and improving the openness of the lid. As these inorganic particles, so-called lubricants can be applied. On the other hand, when a method of directly extruding a molten resin onto a metal base material to produce a resin-coated metal plate (also referred to as a direct coat or the like) is adopted, stable production is performed even when the inorganic particles are not contained in the lower layer. Is possible.
  • aliphatic hydrocarbons higher aliphatic alcohols, fatty acids, fatty acid metal salts, ester or amide derivatives of fatty acids, for example, stearic acid amide, oleic acid amide, erucic acid amide, erucic acid amide, behenic acid amide.
  • Organic lubricants such as ethylene bisoleic acid amide, or silica-based such as silicon dioxide, aluminum silicate, magnesium silicate, general inorganic lubricants such as zeolite, calcium carbonate, silicon dioxide, aluminum oxide, barium sulfate, etc. Commercially available lubricants can be used.
  • the average particle size of these inorganic particles is preferably 0.2 ⁇ m to 5.0 ⁇ m, and more preferably 1.0 ⁇ m to 3.0 ⁇ m.
  • the content of these inorganic particles is preferably 0.1 to 5.0% by mass, preferably 0.4 to 3.0% by mass in the lower copolymer polyester resin in the present embodiment. Is even more preferable.
  • the lower layer 10 of the present embodiment preferably has a breaking elongation of 50% or less in an environment of 50 ° C. after heat treatment at 185 ° C. for 10 minutes. That is, the laminated polyester resin-coated metal plate of the present embodiment is heat-treated at the time of printing or retorting at the time of manufacturing the can lid. Generally, in resins, it is known that the elongation at break after heat treatment is lower than the elongation at break before heat treatment. In the present invention, when the film breaking elongation of the lower layer 10 under a specific temperature (under a 50 ° C. environment) is 50% or less after the heat treatment under the above conditions, even in an area where the temperature is high in the obtained can lid. It has been found that it is possible to secure stable openness and to achieve both problems such as workability.
  • the upper layer 20 of the laminated polyester resin-coated metal plate 100 of the present embodiment will be described.
  • the upper layer 20 is formed on the opposite side of the above-mentioned lower layer 10 from the metal base material MP.
  • the lower layer 10 and the upper layer 20 are formed in this order from the metal base material MP. It can also be said that when the lower layer 10 is in the middle, the metal base material MP is formed on one surface and the upper layer 20 is formed on the other surface.
  • the can lid is manufactured so that the upper layer 20 is on the content side of the can.
  • the resin composition of the upper layer 20 contains a polyester resin (B) as a main agent and a softening component (C) that is incompatible with the polyester resin (B).
  • the content of the soft component (C) is 2 to 50% by mass when the total of the polyester resin (B) and the soft component (C) is 100% by mass. be.
  • the component having the highest content (mass ratio) is defined as the main agent.
  • the content of the soft component (C) is less than 2% by mass, the processability of the laminated polyester resin-coated metal plate of the present embodiment may decrease, which is not preferable.
  • the content of the soft component (C) exceeds 50% by mass, the openness of the can lid may decrease, which is not preferable.
  • the content of the softening component (C) is more preferably 5 to 20% by mass.
  • the polyester resin (B) is preferably a thermoplastic polyester resin from the viewpoint of heat resistance and impact resistance.
  • the thermoplastic polyester resin include polyethylene terephthalate (PET), polyethylene isophthalate, and isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, and diphenoxyethane.
  • Aromatic dicarboxylic acids such as dicarboxylic acid, diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid and phthalic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid and fumaric acid, cyclohexane
  • Dicarboxylic acid components such as alicyclic dicarboxylic acids such as dicarboxylic acids; aliphatic glycols such as ethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and neopentylglycol.
  • thermoplastic resin examples thereof include polyester obtained by copolymerizing aromatic glycols such as bisphenol A and bisphenol S, and alicyclic glycols such as cyclohexanedimethanol. Further, the above-mentioned thermoplastic resin may be used alone or in combination of two or more.
  • thermoplastic polyesters a thermoplastic polyester containing ethylene terephthalate and / or ethylene isophthalate as a main component is preferable from the viewpoint of cost, flavor and the like.
  • the main constituent is 50 mol of the units derived from the terephthalic acid component and the isophthalic acid component, which are dicarboxylic acid components, among the units derived from the total dicarboxylic acid components, among ethylene terephthalate and / or ethylene isophthalate. It means to occupy% or more.
  • thermoplastic polyester used as the polyester resin (B) may be copolymerized with a polyfunctional component selected from a trifunctional or higher functional diprotic acid and a polyhydric alcohol. Due to the copolymerization of the polyfunctional components, the edge (ear) of the film shakes when the film is manufactured at high speed or when the molten film is laminated directly on the metal plate at high speed to manufacture the laminated metal plate. Therefore, draw resonance (ear shaking) in which the film thickness fluctuates is reduced, which is preferable.
  • polyfunctional component selected from trifunctional or higher functional polybasic acids and polyhydric alcohols examples include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, trimethylolpropane, pentaerythritol and the like.
  • the content of these polyfunctional components is 0.01 to 0.5 mol%, preferably 0.07 to 0.3 mol% in the thermoplastic polyester.
  • the draw resonance reducing effect can be appropriately enhanced while suppressing the occurrence of gelation in the thermoplastic polyester.
  • the glass transition temperature (Tg1) of the polyester resin (B) used for the upper layer 20 is preferably 60 ° C. or higher and 90 ° C. or lower, more preferably 65 to 85 ° C., and 70 to 80 ° C. Is more preferable.
  • Tg1 is less than 60 ° C., the heat resistance of the obtained film is lowered and the flavor property may be lowered, which is not preferable.
  • Tg1 exceeds 90 ° C., the processability and impact resistance of the obtained film may decrease, which is not preferable.
  • a known method can be applied as a method for measuring the glass transition temperature, for example, it can be performed at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the thermoplastic polyester used as the polyester resin (B) preferably has an ultimate viscosity [ ⁇ ] of 0.5 to 1.4 dl / g, more preferably 0.7 to 1.2 dl / g. It is more preferably 0.8 to 1.0 dl / g.
  • incompatible means a state in which the boundary between the polyester resin (B) and the soft component (C) can be observed when the upper layer 20 is observed.
  • the soft component (C) in the upper layer 20 of the present embodiment is finely dispersed when blended (blended) with the polyester resin (B) as the main agent described above, and can form a sea-island structure (phase separation). Is. Further, the soft component (C) can impart rubber elasticity to the polyester resin (B) as a main agent at room temperature. Further, when the soft component (C) is blended (blended) with the polyester resin (B) as the main agent, it is preferable that the soft component (C) has almost no effect on the glass transition temperature (Tg) of the polyester resin (B).
  • polyester-based thermoplastic elastomer and polyolefin can be specifically used as the softening component (C).
  • the polyester-based thermoplastic elastomer used as the softening component (C) preferably has a glass transition temperature (Tg) of room temperature (25 ° C.) or lower, more preferably less than 20 ° C., and 10 ° C. or lower. Those are more preferable.
  • the lower limit of the glass transition temperature (Tg) of the polyester-based thermoplastic elastomer used in the present embodiment is not particularly limited, but is preferably ⁇ 50 ° C. or higher.
  • the structure of the polyester-based thermoplastic elastomer generally consists of a hard segment forming a hard crystal structure and a soft soft segment.
  • the components constituting the hard segment of the polyester-based thermoplastic elastomer used in the present embodiment include terephthalic acid, isophthalic acid, bisphenol A, bisphenol S, 2,6-naphthalenedicarboxylic acid, ethylene glycol, and 1,4-butanediol. And so on.
  • the components constituting the soft segment include aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dimer acid, and aliphatic diols such as 1,6-hexanediol, 1,8 octanediol and 1,10-decanediol.
  • aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dimer acid
  • aliphatic diols such as 1,6-hexanediol, 1,8 octanediol and 1,10-decanediol.
  • Polyethers such as polyethylene glycol and polytetramethylene glycol are mentioned. Among these, polyethers are preferable, and among the polyethers, polytetramethylene glycol is particularly preferable.
  • polyester-based thermoplastic elastomer a polyether ester in which a hard segment made of a dicarboxylic acid and a soft segment made of a polyether unit are bonded via an ester bond can be mentioned.
  • those containing 50% by mass or more of the polyether unit in the polyester-based thermoplastic elastomer are preferable.
  • the content ratio of the polyether unit in the polyester-based thermoplastic elastomer is more preferably 50 to 70% by mass, and when the content of the above-mentioned polyether unit is less than 50% by mass, it is when melt-kneaded with the thermoplastic polyester. , It becomes easy to be compatible with each other, and the heat resistance of the film is lowered, which is not preferable.
  • the molecular weight of the polyether unit (polyether segment) in the polyester-based thermoplastic elastomer is not particularly limited, but those of 500 to 5000 are preferably used. Further, the polyester-based thermoplastic elastomer may be modified with maleic anhydride or the like in order to improve the adhesion to the metal. It should be noted that at least one polyether unit may be contained in the polyester-based thermoplastic elastomer, and a plurality of polyether units may be contained.
  • a particularly preferable polyester-based thermoplastic elastomer in the present embodiment is a resin obtained by copolymerizing polybutylene terephthalate with polytetramethylene glycol (PTMG).
  • PTMG polytetramethylene glycol
  • Polyolefins used as the softening component (C) include low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, poly1-butene, poly4-methyl-1-pentene, and ethylene / propylene copolymers. Examples thereof include random copolymers of ⁇ -olefins such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and chain polyolefin resins such as block copolymers.
  • unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid and their anhydrides in an amount of 2% or less to any of these polyolefins.
  • EVA Ethylene vinyl acetate
  • EVOH ethylene-vinyl alcohol copolymer
  • the melt flow rate (hereinafter, simply referred to as MFR) MFR is preferably 30 g / 10 min or less from the viewpoint of film forming property.
  • an ionomer resin ion-crosslinked olefin copolymer in which a part or all of the carboxyl groups are ion-crosslinked with metal cations can also be used.
  • the ionomer resin is an ionic salt in which some or all of the carboxyl groups in the copolymer of ethylene and ⁇ , ⁇ -unsaturated carboxylic acid are neutralized with metal cations, and the degree of neutralization, that is, ions. Concentration affects its physical properties.
  • the melt flow rate of an ionomer resin (hereinafter, simply referred to as MFR) depends on the ion concentration, and when the ion concentration is high, the MFR is small, and the melting point depends on the carboxyl group concentration. The higher the carboxyl group concentration, the smaller the melting point. Become.
  • the ionomer resin used in the present invention is, of course, not limited to this, but has an MFR of 15 g / 10 min or less, particularly 5 g / 10 min to 0. It is desirable that the temperature is in the range of 5 g / 10 min and the melting point is 100 ° C. or lower, particularly 97 ° C. to 80 ° C.
  • Examples of the metal cation in the ionomer resin include Na +, K +, Li +, Zn +, Z2 +, Mg2 +, Ca2 +, Co2 +, Ni2 +, Mn2 +, Pb2 +, Cu2 + and the like.
  • those neutralized with zinc can be preferably used because the degree of cross-linking is large and the humidity sensitivity is low.
  • some of the residual carboxyl groups that have not been neutralized with metal ions may be esterified with a lower alcohol.
  • the glass transition temperature (Tg1) of the polyester resin (B) and the glass transition temperature (C) after mixing the flexible component (C) with the polyester resin (B) as the main agent Regarding the relationship with Tg2), it is preferable that the following formula (1) is satisfied when the content (mass%) of the soft component (C) in the upper layer 20 is W.
  • ⁇ Tg ⁇ 0.5 ⁇ W ⁇ ⁇ ⁇ (1)
  • ⁇ Tg is an absolute value of the difference between Tg1 and Tg2.
  • the soft component (C) when the soft component (C) is mixed with the polyester resin (B) which is the main component in the upper layer 20, the soft component (C) is an island in the polyester resin (B) of the upper layer. It was found that it constitutes a so-called "sea island structure" dispersed in a shape. In that case, the softening component (C) is incompatible with the polyester resin (B), and by satisfying the above formula (1) with respect to the content of the softening component (C), the softening component is blended. It was found that the change in Tg was also suppressed, thereby satisfying the openness and processability.
  • the soft component (C) is dispersed in an island shape in the polyester resin (B) in the upper layer, and the soft component dispersed in the island shape.
  • the average major axis is 0.1 to 5.0 ⁇ m and the average minor axis is 0.01 to 2 ⁇ m.
  • the dispersed particle size of the soft component is large and the aspect ratio is large, so that the can lid is used. It is not preferable because it may reduce the openness of the product.
  • the laminated polyester resin film of the present embodiment includes a light stabilizer, an impact resistance improver, a compatibilizer, a lubricant, a plasticizer, an antistatic agent, a reaction catalyst, a color inhibitor, a radical prohibitor, a plasticizer, an antistatic agent, and the like.
  • Additives such as end-blocking agents, antioxidants, heat stabilizers, mold release agents, flame retardants, antibacterial agents, and anti-plasticizers may be added.
  • the thickness of the laminated polyester resin layer 200 in this embodiment is preferably in the range of 10 ⁇ m to 50 ⁇ m.
  • the thickness of the laminated polyester resin layer 200 exceeds 50 ⁇ m, it is not preferable from the viewpoint of economy and openness.
  • the thickness of the laminated polyester resin layer 200 is less than 10 ⁇ m, the processability and barrier properties when molding into a can lid may be deteriorated, which is not preferable.
  • each layer is not limited to this, but the upper layer 20 is preferably in the range of 5 ⁇ m to 40 ⁇ m, particularly 5 to 15 ⁇ m. If the upper layer 20 is less than 5 ⁇ m, the workability when molding into a can lid may be deteriorated, which is not preferable.
  • the lower layer 10 is preferably in the range of 5 ⁇ m to 30 ⁇ m, particularly preferably 10 to 25 ⁇ m. If the lower layer 10 is less than 5 ⁇ m, the openness of the can lid may decrease, which is not preferable.
  • the laminated polyester resin layer 200 of the present embodiment may include a layer other than the above-mentioned lower layer 10 and upper layer 20. That is, as described above, when the laminated polyester resin layer 200 of the present embodiment is applied to the can lid, the can lid is preferably manufactured so that the upper layer 20 is closer to the contents of the can. be.
  • the surface layer 30 made of polyester resin can be provided on the side of the upper layer 20 opposite to the metal base material side (the content side of the can).
  • the barrier property of the film can be improved.
  • the surface layer 30 for the purpose of improving the flavor property, that is, for avoiding the change in flavor of the can contents or the adsorption of the aroma component contained in the can contents.
  • a polyethylene terephthalate layer is preferable as the surface layer 30 in the present embodiment.
  • the polyethylene terephthalate layer to be the surface layer 30 may contain a copolymerization component, and may contain, for example, 5 mol% or less of isophthalic acid.
  • the thickness of such a surface layer 30 is preferably in the range of 0.1 to 10 ⁇ m.
  • the laminated polyester resin-coated metal plate 100 of the present invention can be manufactured by a method (direct extrusion method) in which a molten resin film is directly extruded onto a metal base material MP, passed between laminate rolls, and pressed and integrated. At this time, an extruder for the upper layer resin and an extruder for the lower layer resin are used, and the resin flows from each extruder are merged in the multi-layer die so that the lower layer resin is on the metal base material side. It can be manufactured by extruding the resin from the die into a thin film.
  • the manufacturing method of the laminated polyester resin-coated metal plate 100 is not limited to the above.
  • it can also be produced by producing a film having a lower layer 10 and an upper layer 20 by a known method, and then heat-adhering the film to the metal base material MP so that the lower layer 10 is on the metal base material MP side. can.
  • the laminated polyester resin film in the present embodiment can be produced by a known method as described above. For example, using an extruder for resin as the upper layer 20 and an extruder for resin as the lower layer 10, the resin flows from each extruder are merged in a multi-layer die, and the resin is thinned from the T-die.
  • a laminated polyester resin film can be obtained by extruding and then winding it by a known method.
  • the laminated polyester resin-coated metal plate 100 can be manufactured by thermally adhering the lower layer 10 to the metal base material MP so that the lower layer 10 is on the metal base material MP side using the laminated polyester resin film of the present embodiment. ..
  • the can lid of the present embodiment can be formed by using the above-mentioned laminated polyester resin-coated metal plate 100 so that the surface on which the above-mentioned lower layer 10 and upper layer 20 are formed becomes the inner surface side of the can lid.
  • the shape of the can lid of the present embodiment can be a known pull-open type or stay-on tab type easy-open lid. Since a known method can be applied to the method for manufacturing the can lid, the description thereof will be omitted here.
  • TFS titanium-free steel having a plate thickness of 0.22 mm
  • the upper and lower resin materials shown in Table 1 were supplied to a twin-screw extruder, and the barrel and T-die were extruded at a temperature suitable for the resin material to obtain a film, and the film was heated to 250 ° C. above.
  • a laminated polyester resin-coated metal plate was obtained by laminating on an aluminum alloy plate and immediately cooling with water. At this time, the thickness of the resin on the inner surface of the lid was set to the thickness shown in Table 2.
  • the obtained single-sided laminate material was painted on the outer surface side of the lid, and then painted and baked at 185 ° C. for 10 minutes.
  • a lid is formed from a blank having a diameter of 95.0 mm, and score processing (residual pressure 75 ⁇ m), rivet processing, attachment of an opening tab, and a lid are attached to this from the outer surface of the lid. Created.
  • Tg Glass transition temperature
  • Example 1 to 10 ⁇ Examples 1 to 10>
  • a thermoplastic elastomer polytetramethylene glycol copolymer polybutylene terephthalate
  • TMA trimellitic acid
  • Example 9 a lubricant was added to the lower layer.
  • polyolefin MFR: 0.9, melting point 80 ° C., Zn-crosslinked ionomer
  • Example 11 had a three-layer structure in which a 2.0 ⁇ m PET / IA2 (isoisophthalic acid 2 mol% copolymerized polyethylene terephthalate resin) layer was formed on the surface layer.
  • the laminated polyester resin film, the laminated polyester resin-coated metal plate, and the can lid of the present invention all have excellent openness and processability.
  • Comparative Examples 1 to 6 For Comparative Examples 1 to 3, a conventionally known two-layer film was applied. Further, in Comparative Examples 4 to 6, the configurations of the lower layer and the upper layer of the present invention were reversed. The laminated polyester resin film, the laminated polyester resin-coated metal plate, and the can lid shown in the comparative example did not have both openness and processability.
  • the present invention can satisfy product requirements while dealing with complicated and harsh lid making processing, and can be suitably used in the field of metal processing.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
PCT/JP2021/011836 2020-04-03 2021-03-23 積層ポリエステル樹脂被覆金属板、積層ポリエステル樹脂フィルム、及び缶蓋 WO2021200358A1 (ja)

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US17/907,447 US20230132293A1 (en) 2020-04-03 2021-03-23 Multilayered polyester resin-coated metal sheet, multilayered polyester resin film, and can lid
EP21779255.5A EP4129647A4 (en) 2020-04-03 2021-03-23 LAYERED POLYESTER RESIN COATED METAL PLATE, LAYERED POLYESTER RESIN FILM AND CAN LID
CN202180021038.5A CN115298025A (zh) 2020-04-03 2021-03-23 层叠聚酯树脂被覆金属板、层叠聚酯树脂膜和罐盖

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